Photo atomic layer deposition of transparent conductive ZnO films

Low-resistivity ZnO films were grown by photo atomic layer deposition (photo-ALD) technique using diethylzinc (DEZ) and H₂O as reactant gases. Self-limiting growth was achieved for the temperature range from 105°C to 235°C. It was found that UV light irradiation was very effective to increase the electron concentration of the films and the electron concentration of 5 × 10²⁰ cm⁻³ was achieved even in undoped ZnO. Thus, the resistivity of the films grown with UV irradiation was one order of magnitude less than that grown without UV irradiation. The minimum resistivity of 6.9 × 10⁻⁴Ω cm was obtained by photo- ALD method without any intentional doping.     

The electro-optical properties of amorphous indium tin oxide films prepared at room temperature by pulsed laser deposition

The electrical and optical properties of pulsed laser deposited amorphous indium tin oxide films at room temperature are discussed. The films were grown from indium oxide (In₂O₃) targets of different tin (Sn) doping content (0, 5 and 10 wt%) at different oxygen pressures (P_O2) ranging from 1×10⁻³ to 5×10⁻² Torr. The electrical and optical properties of the films were examined by Hall measurements and optical spectrophotometry. It was found that high conductivity amorphous films could be prepared at room temperature irrespective of the Sn doping content. The properties of these films deposited from 0, 5, 10 wt% Sn-doped In₂O₃ targets show a similar response to changes in P_O2. The maximal conductivity of (4.0, 2.1 and 1.8)×10³ S/cm and optical transmittance (visible) higher than 90% were obtained at P_O2 region of (1–1.5)×10⁻² Torr. An undoped In₂O₃ film produced the highest conductivity of 4×10³ S/cm in these studies.     

Growth and characterization of lead sulfide films deposited on glass substrates

Lead sulfide (PbS) films have been deposited by chemical deposition on a glass substrate. Microstructure characterization was carried out by X-ray diffraction and scanning electron microscopy in order to determine the average crystallite size (15 nm) and study the surface morphologies of the as-deposited and heat-treated films. The PbS films obtained had p-type conductivity and low resisitivity (5 Ω cm). The carrier density, Hall mobility and mean free path of carriers in PbS films were in the range 2.5×10¹⁷ cm⁻³, 5 cm²/V s and 0.642 μm, respectively.     

Promotion of microcrystallization by argon in moderately hydrogen diluted silane plasma

Using argon as a diluent of SiH₄, undoped hydrogenated microcrystalline silicon (μc-Si:H) films, having σ_D10⁻⁵ S cm⁻¹, were prepared at a very high deposition rate of 36 Å/min. Micrograins were identified with several well-defined crystallographic orientations. The effect of variation of Ar-dilution on the electrical and structural properties of Si:H films were studied systematically. Addition of H₂ to the Ar-diluted SiH₄ plasma improved the network structure by eliminating defects, introducing structural reorientation and grain growth, although, reducing the deposition rate. Accordingly, highly conducting (σ_D10⁻³S cm⁻¹) undoped μc-Si:H film was achieved utilizing energy released by de-excitation of metastable state of Ar (denoted as Ar*), in association with network modulation by atomic hydrogen in the plasma.     

Properties of p-type amorphous silicon carbide window layers prepared using boron trifluoride

One set (A) of undoped and three sets (B, C and D) of doped hydrogenated amorphous silicon carbide samples have been made in the framework of a research plan for obtaining high quality p-type window layers by radiofrequency glow discharge of silane-based gas mixtures. The samples of sets A and B were made using different RF-power-density to mass-flow ratios for various methane percentages in the gas mixture. The best carbon incorporation in the amorphous silicon lattice was obtained at the highest RF-power density. The properties of sets C and D, prepared using different RF-power densities and silane and methane propertions have been analysed as functions of the concentration of borom trifluoride with respect to silane. In both cases, the optical gap E_G, after a slight initial decrease, remains at a value of approximately 2.1 eV without quenching in the dopiong ranges covered. The best conductivity obtained is 2 × 10⁻⁷ (μ cm)⁻¹. IR spectra allow to associate these features with the structural quality of the films.     

Effect of proton irradiation on electrical properties of CuInSe2 thin films

High-energy proton irradiation (380 keV and 1 MeV) on the electrical properties of CuInSe₂ (CIS) thin films has been investigated. The samples were epitaxially grown on GaAs (0 0 1) substrates by Radio Frequency sputtering. As the proton fluence exceeded 1×10¹³ cm⁻², the carrier concentration and mobility of the CIS thin films were decreased. The carrier removal rate with proton fluence was estimated to be about 1000 cm⁻¹. The electrical properties of CIS thin films before and after irradiation were studied between 80 and 300 K. From the temperature dependence of the carrier concentration in CIS thin films, we found N_D=9.5×10¹⁶ cm⁻³, N_A=3.7×10¹⁶ cm⁻³ and E_D=21 meV from the fitting to the experimental data on the basis of the charge balance equation. After irradiation, a defect level was created, and N_T=1×10¹⁷ cm⁻³ for a fluence of 3×10¹³ cm⁻², N_T=5.7×10¹⁷ cm⁻³ for a fluence of 1×10¹⁴ cm⁻² and E_T=95 meV were also obtained from the same fitting. The new defect, which acted as an electron trap, was due to proton irradiation, and the defect density was increased with proton fluence.     

Structural properties of phosphorous-doped polycrystalline silicon

The structural properties and hydrogen bonding of undoped and phosphorous doped polycrystalline silicon produced by step-by-step laser dehydrogenation and crystallization technique were investigated using Raman spectroscopy and hydrogen effusion measurements. At low laser fluences, E_L, a two-layer system is created. This is accompanied by the change in hydrogen bonding. The intensity of the Si–H vibration mode at 2000 decreases faster than the one at 2100 cm⁻¹. This is even more pronounced in phosphorous-doped specimens. The laser crystallization results in an increase of the hydrogen binding energy by approximately 0.2–0.3 eV compared to the amorphous starting materials.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Investigation of non-aqueous electrodeposited CdS/Cd1−xZnxTe heterojunction solar cells

Polycrystalline Cd_1−xZn_xTe solar cells with efficiency of 8.3% were grown by cathodic electrodeposition on glass/ITO/CdS substrates using non-aqueous ethylene glycol bath. The deposit is characterised versus the process conditions by XRD and found to possess a preferred (1 1 1) orientation on Sb doping in the electroplating bath. The surface morphology of the deposit is studied using atomic force microscope. The average RMS roughness for the ternary film was higher than that for the binary CdTe. Optical properties of the films were carried out to study the band gap and calculation of molar concentration ‘x’. The effects of Sb doping in CdS/Cd_1−xZn_xTe heterojunctions have been studied. The short circuit current density (c) was found to improve and series resistance (R_s) reduced drastically upon Sb doping. This improvement in J_sc is attributed to an increase in quantum efficiency. The evaluation of solar cell parameters was also carried out using the current–voltage characteristics in dark and illumination. The best results were obtained when 2×10⁻³ M ZnCl₂ along with antimony were present in the deposition bath. Under AM 1.5 conditions the open circuit voltage, short circuit current density, and fill factor of our best cell were V_oc=600 mV, J_sc=26.66 mA/cm², FF=0.42 and efficiency, η=8.3%. The carrier concentration and built-in potential of Cd_1−xZn_xTe calculated from Mott–Schottky plot was 2.72×10¹⁷ cm⁻³ and 1.02 eV.     

Diffusion and influence of Cu on properties of CdTe thin films and CdTe/CdS cells

The effective diffusion coefficients of Cu for thermal and photodiffusion in the CdTe films have been estimated from resistivity versus duration of thermal or photoannealing curves. In the temperature range 60–200°C the effective coefficient of thermal diffusion (D_t) and photodiffusion (D_ph) are described as D_t=7.3×10⁻⁷exp(−0.33/kT) and D_ph=4.7×10⁻⁸exp(−0.20/kT).It is found that the diffusion doping of CdTe thin films by Cu at 400°C results in a sharp decrease of resistivity up to 7 orders of magnitude of p-type material, depending on thickness of Cu film. The comparative study of performance of CdTe(Cu)/CdS and CdTe/CdS cells has been studied. It is shown that the diffusion doping of CdTe film by Cu increases efficiency of CdTe(Cu)/CdS cells from 0.9% to 6.8%. The degradation of photovoltaic parameters of CdTe(Cu)/CdS cell, during testing under forward and reverse bias at room temperature, proceeds at a larger rate than those of CdTe/CdS cell without Cu. The degradation of performance of CdTe(Cu)/CdS cells is tentatively assigned to electrodiffusion of Cu in CdTe, resulting in redistribution of concentration of Cu-related centers in CdTe film and heterojunction region.     

Photoelectrical properties of doped cadmium sulphide powders

Photosensitive powders of CdS were prepared with different concentrations of dopants. Doses of donors (Cl⁻) and acceptors (Cu²⁺, Ag⁺) varied from 0 to 41 and from 0 to 9 mg/g CdS, respectively. Reflectance, absorption coefficient and resistance dependence on illumination intensity and voltage at the wavelength of about λ=630 nm and photovoltage spectra in the range 450–900 nm were measured on layers prepared from the powders. The value of absorption coefficient grew with the increasing dopant concentrations; acceptors appeared more efficient than donors. Reflectance decreased with growing acceptor dose. Using the values of reflectance, absorption coefficient and resistance the corrected photovoltage, as the measure of the concentration photogenerated charge carriers, was calculated. The ratio (σ_IGB) of the corrected photovoltage and photocurrent was used as the criterion of intergrain barrier conductivity. All doped samples exhibited similar value of σ_IGB which was about three orders of magnitude lower than that of undoped sample.     

Temperature effect on the electrical properties of undoped and vanadium-doped ZnTe thin films

Vanadium-doped ZnTe films of composition 0 to 10 wt% V, were prepared onto glass substrate by e-beam evaporation of the element in vacuum at 8×10⁻⁴ Pa. The effects of various deposition conditions on the electrical properties of the films have been studied in detail. The deposition rate of the ZnTe films was at about 2.05 nm s⁻¹. X-ray diffraction (XRD) study shows that the as-deposited ZnTe films are amorphous in nature.The effects of temperature on the electrical properties of the ZnTe and ZnTe:V films were studied in details. The heating and cooling cycles of the samples are reversible in the investigated temperature range after successive heat treatments in air. Thickness dependence of electrical conductivity is well in conformity with the Fuchs–Sondheimer theory. Temperature dependence of electrical conductivity shows a semiconducting behavior with a spectrum of activation energy. The value of activation energy for undoped ZnTe films do agree well with earlier reported values. Dopant vanadium concentration increases the conductivity of the samples. The composition and thickness dependence of the activation energy as well as thermoelectric power studies were done in the 300–413 K temperature range. The results of d.c. conductivity and thermopower obey an activated conduction mechanism. The thermopower of undoped ZnTe films indicates a p-type conductivity. Thermopower results of ZnTe:V films also suggest that the simultaneous bipolar conduction of both carriers take place.     

Development of thermoelectric oxides for renewable energy conversion technologies

Geothermal and solar heat can be directly converted into electricity by using thermoelectric generators. Perovskite-type metal oxides are potential materials to improve the efficiency of these devices. Cobaltates with p-type conductivity and n-type manganates are considered for the development of a ceramic thermoelectric converter.Sintered pellets and thin PLD films with the composition La_1−xCa_xMO_3−δ (x=0, 0.3, 0.4) (M = Co, Mn) were synthesised and characterised concerning their thermoelectric properties in a broad temperature range. It was found that similar to polycrystalline samples the electrical conductivity of LaCoO₃ increases significantly with 40% Ca-substitution due to the formation of Co⁴⁺ ions while the thermopower decreases. The thermopower values of the La_0.8Ca_0.2MnO_3−δ films have a negative sign, but become large and positive at temperatures of 1000 K.     

Effect of 8 MeV electron irradiation on electrical properties of CuInSe2 thin films

Radiation damages due to 8 MeV electron irradiation in electrical properties of CuInSe₂ thin films have been investigated. The n-type CuInSe₂ films in which the carrier concentration was about 3×10¹⁶ cm⁻³, were epitaxially grown on a GaAs(0 0 1) substrate by RF diode sputtering. No significant change in the electrical properties was observed under the electron fluence <3×10¹⁶ e cm⁻². As the electron fluence exceeded 10¹⁷ e cm⁻², both the carrier concentration and Hall mobility slightly decreased. The carrier removal rate was estimated to be about 0.8 cm⁻¹, which is slightly lower than that of III–V compound materials.     

Fabrication of stable hydrogenated amorphous silicon from SiH2Cl2 by ECR-hydrogen-plasma

Relatively stable high bandgap hydrogenated amorphous silicon (a-Si:H) films were prepared by the microwave electron cyclotron resonance (ECR) hydrogen plasma CVD method using SiH₂Cl₂ source gas. The substrate position relative to the position of the generation of reactive species affects the structure of these films. The films prepared under optimized condition showed rather high bandgap, 1.83 eV. However, the defect density was low, 3 × 10¹⁵ cm⁻³, and the photosensitivity was greater than 7 orders of magnitudes. The defect density was found to saturate at relatively low values ( 3 × 10¹⁶ cm⁻³) independent of the illumination intensity.     

Electrical and optical properties of thin films based on poly [2-methoxy-5 (2′-ethyl hexyloxy)-1,4-phenylene vinylene] doped with acridine orange dye with possible photovoltaic applications

Conjugated polymers have high potential for efficient production of low-cost flexible optoelectronics devices such as solar cells, photodiodes and light emitting diodes. In this paper, the interaction between poly [2-methoxy-5 (2′-ethyl hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and acridine orange (AO) dye has been studied to examine the role of charge pair separation and photocurrent generation in organic photovoltaic films. The AO dye concentration has been optimized on the basis of absorption spectra and photoluminescence (PL) studies carried over the films particularly, for photovoltaic applications. For this purpose, MEH-PPV polymer was dissolved in n-butyl acetate and doped with different concentration of AO dye solution. The Current–Voltage characteristics of MEH-PPV films, prepared by spin-coating technique on ITO-coated glass substrate have been determined as a function of temperature. For the cathode contact, Al was deposited using RF sputtering technique so that the current is predominantly due to holes. The conductivity increases by two orders of magnitude as the AO dye concentration increases to 2.65 mol L⁻¹. In optical properties, we have studied the UV–visible absorption spectra, PL spectra of undoped and doped MEH-PPV films. The absorption studies show that the addition of AO dye does not significantly change (reduce) the absorption, which indicates the suitability of photon absorption. The PL spectra were recorded for MEH-PPV films, which become narrow on increasing the AO dye concentration. The PL studies indicate that up to certain concentration of AO dye in MEH-PPV films, PL intensity decreases as compare to that for undoped MEH-PPV film. The combined effect of increase in conductivity by two orders, decrease in PL intensity and no significant change in absorption makes the material suitable for photovoltaic applications.     

Preparation and study of structural and optical properties of CSVT deposited CuInSe2 thin films

A simple close-spaced vapour transport (CSVT) system has been designed and fabricated. Copper indium diselenide (CuInSe₂) thin films of wide range of thickness (4000–60000 Å) have been prepared using the fabricated CSVT system at source temperatures 713, 758 and 843 K. A detailed study on the deposition temperature has been made and the temperature profile along with the reaction kinetics is reported. The composition of the chemical constituents of the films has been determined by energy dispersive X-ray analysis. The structural characterization of the as-deposited CuInSe₂ films of various thicknesses has been carried out by X-ray diffraction method. The diffractogram revealed that the CuInSe₂ films are polycrystalline in nature with chalcopyrite structure. The structural parameters such as lattice constants, axial ratio, tetragonal distortion, crystallite size, dislocation density and strain have been evaluated and the results are discussed. The surface morphology of the as-deposited CuInSe₂ thin films has been studied using scanning electron microscope. The transmittance characteristics of the CuInSe₂ films have been studied using double beam spectrophotometer in the wavelength range 4000–15000 Å and the optical constants n and k are evaluated. The absorption coefficient has been found to be very high and is of the order of 10⁵–10⁶ m⁻¹. CuInSe₂ films are found to have a direct allowed transition and the optical band gap is found to be in the range 0.85–1.05 eV.     

Thermophilic bio-energy process study on hydrogen fermentation with vegetable kitchen waste

An intermittent-continuous stirred tank reactor (I-CSTR) was evaluated for thermophilic anaerobic hydrogen fermentation with vegetable kitchen waste (VKW). The seeding sludge was enriched from kitchen waste compost. Because of different seasonal dietary habits, the quality of vegetable kitchen waste was unstable, and all variations of composition were in the range from 20 to 40%. The I-CSTR process was conducted under different volumetric loading rates (VLR) with different VKW-diluted concentrations. The hydrogen production rate and yield in Run 2 (VLR as 28 g-COD L⁻¹ day⁻¹) were 1.0 L-H₂ L⁻¹ day⁻¹ and 1.7 mmol-H₂ g-COD⁻¹, which were higher than those in Run1 (VLR as 19 g-COD/L-day). The hydrolysis efficiency of organic solids (VSS) was about 45% in Run 1 better than the 32% in Run 2. The carbohydrate component of VKW was clearly degraded with the accumulation of butyrate, while the organic nitrogen component was converted to ammonia. The vegetable cellulose was degraded from 3.2 g L⁻¹ and 3.6–1.8 and 3.2 g L⁻¹ in Runs 1 and 2, respectively. In addition, the high concentration of lactate from the acidified VKW could be degraded completely both in Runs 1 and 2. According to the results of the time series profile in day 59, oil and grease were not degraded significantly. The removal of oil and grease was superficially caused by stacking on the wall, pipe, and propeller of the reactor, or by floating on the liquid surface. The 16S rDNA cloning library and sequence were applied for analyzing microbial communities. The dominant OTU was closely affiliated to Thermoanaerobacterium thermosaccharolyticum, which is considered as the predominant hydrogen-producing bacteria. The OTUs closely related to Moorella thermoacetica and Clostridiaceae bacterium FH052 were considered as acetogenic bacterium and hydrogen-producing bacteria in the I-CSTR system.     

Composition, surface topography, structure, Raman, and electrochemical/photoelectrochemical characterisation of CdxHg1−xTe films

Cd-rich Cd_xHg_{1 − x}Te films have been electrodeposited under potentiostatic conditions on conducting glass and Ti substrates from an acidic solution containing the respective ions as Cd²⁺:Hg²⁺:HTeO₂⁺ = 100:1:2. Six films one after another have been prepared from a single electrochemical cell. EDAX analysis of the air annealed films show decreasing Hg content in the deposit as the number of film preparation increases. SEM analysis indicate undulatory surface with Hg-rich clusters at the top surface. XRD analysis indicate the presence of Cd_xHg_{1 − x}Te along with . The Cd_xHg_{1 − x}Te alloy formation have been confirmed from Raman shift measurements which change with composition, x. The as-deposited films are n-type but converts to p-type after air annealing. Spectral response measurements gave band gap values that change with Hg content in the deposit. Band gap values ranging from 1.1 eV to 1.45 eV have been estimated. Photoelectrochemical solar cells using polysulphide electrolyte have been fabricated which gave an open-circuit photovoltage and short-circuit photocurrent, respectively, as 325 mV and 5.5 mA/cm² under 60 mW/cm² intensity of illumination.     

Highly conducting transparent nanocrystalline Cd1−xSnxS thin film synthesized by RF magnetron sputtering and studies on its optical, electrical and field emission properties

Transparent conducting Cd_1−xSn_xS thin films have been synthesized by radio frequency magnetron sputtering technique on glass and Si substrates for various tin concentrations in the films. X-ray diffraction studies showed broadening of peaks due to smaller crystal size of the Cd_1−xSn_xS films, and SEM micrographs showed fine particles with average size of 100 nm. Sn concentration in the films was varied from 0% to 12.6% as determined from energy-dispersive X-ray analysis. The room-temperature electrical conductivity was found to vary from 8.086 to 939.7 S cm⁻¹ and corresponding activation energy varied from 0.226 to 0.076 eV. The optimum Sn concentration for obtaining maximum conductivity was found to be 9.3%. The corresponding electrical conductivity was found to be 939.7 S cm⁻¹, and the mobility 49.7 cm² V⁻¹ s⁻¹. Hall measurement showed very high carrier concentrations in the films lying in the range of 8.0218×10¹⁸–1.7225×10²⁰ cm⁻³. The conducting Cd_1−xSn_xS thin films also showed good field emission properties with a turn on field 4.74–7.86 V μm⁻¹ with variation of electrode distance 60–100 μm. UV–Vis–NIR spectrophotometric studies of the films showed not needed the optical band gap energy increased from 2.62 to 2.80 eV with increase of Sn concentration in the range 0–12.6%. The optical band gap was Burstein–Moss shifted, and the corresponding carrier concentration obtained from the shift also well matched with that obtained from Hall measurement.